CN102728400A - Catalyst for preparing cyanamide by dehydrating urea and its preparation method - Google Patents
Catalyst for preparing cyanamide by dehydrating urea and its preparation method Download PDFInfo
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- CN102728400A CN102728400A CN2011101041429A CN201110104142A CN102728400A CN 102728400 A CN102728400 A CN 102728400A CN 2011101041429 A CN2011101041429 A CN 2011101041429A CN 201110104142 A CN201110104142 A CN 201110104142A CN 102728400 A CN102728400 A CN 102728400A
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Abstract
The invention discloses a catalyst for preparing cyanamide by dehydrating urea and its preparation method. The invention relates to a bimetallic active ingredient molecular sieve catalyst, its composition can be expressed as M1-M2-Z, an active ingredient M1 is one or more selected from transition metal elements of Mn, Fe, Cu and Co; an active ingredient M2 is one or more selected from transition metal elements of Mn, Fe, Cu and Co and rare earth element of La and Ce; the molecular sieve Z is one or more selected from ZSM-5 type, Y type and beta type, wherein the ZSM-5 type molecular sieve can be H type or Na type, and the ratio of Si to Al is 25-200. The mass of the catalyst comprises 0.5-10% of M1, 0.05-2% of M2 and 88-99.45% of Z. because the second metal active ingredient is added, the catalyst structure is changed, in the process of preparing cyanamide by catalyzing and dehydrating urea, the generation of the by-product can be substantially minimized, and the selectivity of cyanamide can be increased. The catalyst can be used for preparing cyanamide by dehydrating urea, and can be operated in a fixed bed and a fluidized bed reactor.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used for catalyzing urea dehydration system cyanamide, this catalyst is a kind of bimetallic active component catalyst, and reactivity is good, and selectivity is high.
Background technology
Cyanamide is a kind of important chemical material, organic chemical industry's intermediate, and still a kind of very important medical material also can be used as noresidue, low toxicity, phosphoramidite chemical pesticide intermediate.In addition, cyanamide also can be used for synthesizing of health product, feed addictive and fire retardant etc., and purposes is very extensive.The industrial process of cyanamide mainly is the lime nitrogen method, this method complex manufacturing, and equipment investment is big, seriously polluted, energy consumption is high, contains more free state calcium carbide in the product.Raw material lime nitrogen (claiming nitrolim again) is made by the calcium carbide high-temperature ammonolysis.The production of lime nitrogen itself is exactly the conventional industries of a highly energy-consuming, high pollution, maximum discharge.In order to overcome the defective of this technology, it is raw material that Jens Weitkamp etc. propose with urea (urea) in the US5166432 patent, dehydration preparation cyanamide under the zeolite molecular sieve of carrying transition metal or aluminium silicophosphate molecular sieve catalyst action.It is that 0.3nm～molecular sieve carried transition metal component of 0.5nm micropore ZSM-5 such as copper, manganese etc. are as catalyst that this patent adopts diameter; The molecular sieve silica alumina ratio is 2～120; The control temperature is at 450 ℃～550 ℃; The urea transformation rate reaches more than 60%, and accessory substance mainly is dicyandiamide, cyanamide urea, guanidine carbonate and melamine.This is that relatively more green process route, raw material sources are wide, cheap; But this process byproducts is more, and selectivity is also lower, and therefore follow-up separation and refining cost are higher.
Summary of the invention
The object of the invention be to provide a kind of active high, selectivity is strong, accessory substance is few, long service life, cost are low, are used for the bicomponent catalyst and the preparation technology thereof of catalyzing urea dehydration preparation cyanamide.
Technical solution of the present invention can realize according to following mode:
Catalyst of the present invention is a kind of modified molecular sieve catalyst with bimetallic active component, forms through ion-exchange or immersion process for preparing.Its structure can be expressed as M
1-M
2-Z, active component M
1Be among transition metal Mn, Fe, Cu, the Co one or more, active component M
2Be among transition metal Mn, Fe, Cu, Co and rare-earth metals La and the Ce one or more; Molecular sieve Z is one or more in the molecular sieve in ZSM-5 type, Y type and the β type, and wherein type ZSM 5 molecular sieve can be H type or Na type, and the Si/Al ratio is 25～200.Catalyst quality consists of: M
1Account for 0.5%～10%, M
2Account for 0.05%～2%, Z accounts for 88%～99.45%.Its preparation technology is:
1. ion-exchange
1.1 take by weighing a certain amount of molecular sieve, be 550 ℃ in temperature and baked 3～8 hours, remove moisture and other absorption impurity in the hole;
1.2 dispose certain density M
1And M
2The acetate of element or nitrate precursor solution;
1.3 two kinds of elements adopt exchange simultaneously, or the method for exchange respectively prepares the bimetal element catalyst, the exchange number of times is 1～3 time;
1.4 filter, wash, following dry 12 hours at 120 ℃ then;
1.5 add a small amount of sesbania powder, and with mixes with small amount of water moulding, oven dry;
1.6 before using under nitrogen atmosphere, 500 ℃～700 ℃ following roastings 8～12 hours.
2. infusion process
2.1 take by weighing a certain amount of molecular sieve, be 550 ℃ in temperature and baked 3～8 hours, remove moisture and other absorption impurity in the hole;
2.2 dispose certain density M
1And M
2The acetate of element or nitrate precursor solution;
2.3 two kinds of elements can adopt common dipping, or the method for dipping prepares the bimetal element catalyst respectively;
2.4 filter, wash, following dry 12 hours at 120 ℃ then;
2.5 add a small amount of sesbania powder, and with mixes with small amount of water moulding, oven dry;
2.6 before using under nitrogen atmosphere, 500 ℃～700 ℃ following roastings 8～12 hours.
The catalyst quality of preparation consists of: M
1Account for 0.5%～10%, M
2Account for 0.05%～2%, Z accounts for 88%～99.45%.
Advantage of the present invention: because the adding of second metal active constituent; Modulation catalyst structure and surface nature; In catalyzing urea dehydration preparation cyanamide process; Significantly reduced production of by-products, improved the selectivity of cyanamide, its accessory substance mainly is a spot of dicyandiamide and melamine.
The evaluation of catalyst is carried out in a volumes is the quartz ampoule fixed bed reactors of 60mL, and loaded catalyst is 30mL.Particle diameter is that the urea granules of 0.2mm～0.3mm is brought reactor by the hold concurrently ammonia of co-catalyst of carrier gas into the fluidization mode, and under normal pressure, reaction temperature is controlled at 450 ℃～700 ℃.Urea at high temperature is decomposed into cyanic acid (or isocyanic acid) and ammonia, and cyanic acid and ammonia react under catalyst action and generate cyanamide and water.Product obtains product through room temperature water condensation and-20 ℃ liquid nitrogen condensation, and product adopts efficient liquid phase chromatographic analysis.
The specific embodiment
Below in conjunction with embodiment the present invention is done further elaboration, but the present invention is not produced any restriction.
Embodiment 1
(1) is that 50 H-ZSM-5 molecular sieve 50g baked under 550 ℃ 4 hours with Si/Al, removes moisture and other absorption impurity in the hole;
(2) configuration 500mL contains the Mn (AC) of 0.2mol/L
2CuSO with 0.01mol/L
4Solution stirs exchange 3 hours down at 80 ℃, carries out ion-exchange 1～3 time respectively, obtains embodiment 1-1, embodiment 1-2 and embodiment 1-3 catalyst respectively;
(3) filter, wash, under 120 ℃, dry 12 hours;
(4) add a small amount of sesbania powder, and with mixes with small amount of water moulding, oven dry;
(5) be 500mL/min at nitrogen flow, 600 ℃ of following roastings 8 hours;
(6) catalyst is at 550 ℃, and ammonia flow is 6L/min, and the urea addition is to estimate under the condition of 10g/h.
Embodiment 2
(1) is that 150 H-ZSM-5 molecular sieve 50g baked under 550 ℃ 4 hours with Si/Al, removes moisture and other absorption impurity in the hole;
(2) configuration 500mL contains the Mn (AC) of 0.2mol/L
2Ce (NO with 0.01mol/L
3)
2Solution stirs exchange 3 hours down at 80 ℃, carries out ion-exchange 2 times;
(3) filter, wash, under 120 ℃, dry 12 hours;
(4) add a small amount of sesbania powder, and with mixes with small amount of water moulding, oven dry;
(5) be 500mL/min at nitrogen flow, 600 ℃ of following roastings 8 hours;
(6) catalyst is at 550 ℃, and ammonia flow is 6L/min, and the urea addition is to estimate under the condition of 10g/h.
Embodiment 3
(1) is that 50 H-ZSM-5 molecular sieve 50g baked under 550 ℃ 4 hours with Si/Al, removes moisture and other absorption impurity in the hole;
(2) configuration 500mL contains the CuSO of 0.2mol/L
4With 0.01mol/L Mn (AC)
2Solution, stir down exchange 3 hours at 80 ℃, carry out ion-exchange 2 times;
(3) filter, wash, under 120 ℃, dry 12 hours;
(4) add a small amount of sesbania powder, and with mixes with small amount of water moulding, oven dry;
(5) be 500mL/min at nitrogen flow, 600 ℃ of following roastings 8 hours;
(6) catalyst is at 550 ℃, and ammonia flow is 6L/min, and the urea addition is to estimate under the condition of 10g/h.
Embodiment 4
(1) 50g NaY molecular sieve was baked under 550 ℃ 4 hours, remove moisture and other absorption impurity in the hole;
(2) configuration 500mL contains the Mn (AC) of 0.2mol/L
2With 0.01mol/L Fe (NO
3)
2Solution, stir down exchange 3 hours at 80 ℃, carry out ion-exchange 2 times;
(3) filter, wash, under 120 ℃, dry 12 hours;
(4) add a small amount of sesbania powder, and with mixes with small amount of water moulding, oven dry;
(5) be 500mL/min at nitrogen flow, 600 ℃ of following roastings 8 hours;
(6) catalyst is at 550 ℃, and ammonia flow is 6L/min, and the urea addition is to estimate under the condition of 10g/h.
Embodiment 5
(1) the 50g beta-molecular sieve was baked under 550 ℃ 4 hours, remove moisture and other absorption impurity in the hole;
(2) adopt equi-volume impregnating, preparation Mn load capacity is 2%, and the La load capacity is 0.5% support type Mn-La/ beta catalyst;
(3) under 120 ℃, dry 12 hours;
(4) add a small amount of sesbania powder, and with mixes with small amount of water moulding, oven dry;
(5) be 500mL/min at nitrogen flow, 600 ℃ of following roastings 8 hours;
(6) catalyst is at 550 ℃, and ammonia flow is 6L/min, and the urea addition is to estimate under the condition of 10g/h.
The result is as shown in table 1 for the embodiment evaluating catalyst.
Table 1
Claims (5)
1. plain a dehydration made the catalyst of cyanamide, it is characterized in that: catalyst is the catalysis of a kind of bimetallic molecules of active components sieve, and it consists of M
1-M
2-Z, active component M
1Be among transition metal Mn, Fe, Cu, the Co one or more; Active component M
2Be among transition metal Mn, Fe, Cu, Co and rare-earth metals La and the Ce one or more; Molecular sieve Z is one or more in the molecular sieve in ZSM-5 type, Y type and the β type; Catalyst quality consists of: M
1Account for 0.5%～10%, M
2Account for 0.05%～2%, Z accounts for 88%～99.45%.
2. according to the catalyst of the described urea dehydration of claim 1 system cyanamide, it is characterized in that: active component M
1Mass content be 1%～8%.
3. according to the catalyst of the described urea dehydration of claim 1 system cyanamide, it is characterized in that: active component M
2Mass content be 0.5%～1%.
4. according to the catalyst of the described urea dehydration of claim 1 system cyanamide, it is characterized in that: type ZSM 5 molecular sieve can be H type or Na type, and the Si/Al ratio is 25～200.
5. the Preparation of catalysts method according to the described urea dehydration of claim 1 system cyanamide is ion-exchange or infusion process.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107715879A (en) * | 2017-10-11 | 2018-02-23 | 四川美丰化工股份有限公司 | A kind of isocyanic acid decomposition method for preparing catalyst and made catalyst application method |
| CN107840811A (en) * | 2017-12-15 | 2018-03-27 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of dicyandiamide |
| CN110304638A (en) * | 2019-08-02 | 2019-10-08 | 山东益丰生化环保股份有限公司 | A method of cyanamide is prepared using urea |
| CN113603557A (en) * | 2021-08-20 | 2021-11-05 | 四川金象赛瑞化工股份有限公司 | Process for co-production of dicyandiamide and ammonium nitrate nitrogen fertilizer |
| CN114887657A (en) * | 2022-06-10 | 2022-08-12 | 宁波中科远东催化工程技术有限公司 | Catalyst for synthesizing melamine and preparation method thereof |
| CN115282952A (en) * | 2022-08-29 | 2022-11-04 | 天津科技大学 | Catalyst for preparing cyanamide by catalyzing urea decomposition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3300281A (en) * | 1965-08-06 | 1967-01-24 | American Cyanamid Co | Method for manufacture of cyanamide |
| US5166432A (en) * | 1990-08-21 | 1992-11-24 | Skw Trostberg Aktiengesellshaft | Process for the production of cyanamide |
| CN101007283A (en) * | 2007-01-26 | 2007-08-01 | 江苏工业学院 | ZSM-5 molecular sieve modified catalyst and its preparation method and application |
-
2011
- 2011-04-15 CN CN2011101041429A patent/CN102728400A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3300281A (en) * | 1965-08-06 | 1967-01-24 | American Cyanamid Co | Method for manufacture of cyanamide |
| US5166432A (en) * | 1990-08-21 | 1992-11-24 | Skw Trostberg Aktiengesellshaft | Process for the production of cyanamide |
| CN101007283A (en) * | 2007-01-26 | 2007-08-01 | 江苏工业学院 | ZSM-5 molecular sieve modified catalyst and its preparation method and application |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107715879A (en) * | 2017-10-11 | 2018-02-23 | 四川美丰化工股份有限公司 | A kind of isocyanic acid decomposition method for preparing catalyst and made catalyst application method |
| CN107840811A (en) * | 2017-12-15 | 2018-03-27 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of dicyandiamide |
| CN110304638A (en) * | 2019-08-02 | 2019-10-08 | 山东益丰生化环保股份有限公司 | A method of cyanamide is prepared using urea |
| CN110304638B (en) * | 2019-08-02 | 2022-06-21 | 山东益丰生化环保股份有限公司 | Method for preparing cyanamide by using urea |
| CN113603557A (en) * | 2021-08-20 | 2021-11-05 | 四川金象赛瑞化工股份有限公司 | Process for co-production of dicyandiamide and ammonium nitrate nitrogen fertilizer |
| CN113603557B (en) * | 2021-08-20 | 2022-10-11 | 四川金象赛瑞化工股份有限公司 | Process for co-production of dicyandiamide and ammonium nitrate nitrogen fertilizer |
| CN114887657A (en) * | 2022-06-10 | 2022-08-12 | 宁波中科远东催化工程技术有限公司 | Catalyst for synthesizing melamine and preparation method thereof |
| CN114887657B (en) * | 2022-06-10 | 2024-01-26 | 宁波中科远东催化工程技术有限公司 | Catalyst for synthesizing melamine and preparation method thereof |
| CN115282952A (en) * | 2022-08-29 | 2022-11-04 | 天津科技大学 | Catalyst for preparing cyanamide by catalyzing urea decomposition |
| CN115282952B (en) * | 2022-08-29 | 2024-05-03 | 天津科技大学 | Catalyst for preparing cyanamide by catalyzing urea decomposition |
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Application publication date: 20121017 |